1. Field of the Invention
The present invention relates to a process for preserving wood and composite wood materials from wood damaging organisms, and compositions useful in such process.
This invention more specifically is directed to a class of 3-aryl-5,6-dihydro-1,4,2-oxathiazines and their oxides which are useful against such wood damaging organisms as bacteria, yeasts, and fungi.
This invention is also directed to novel 3-aryl-5,6-dihydro-1,4,2-oxathiazines and their oxides which are useful against such wood damaging organisms as bacteria, yeasts, and fungi.
2. Description of Related Art
The preservation of wood is a subject of great economic importance. For most purposes, untreated wood is entirely unsatisfactory. It will twist, warp, and crack as it dries; it cannot easily be glued or finished, and it is subject to attack of fungi and/or insects. Properly prepared and preserved wood possesses strength and incompressibility while being flexible.
U.S. Pat. No. 4,569,690 refers to various 3-aryl-5,6-dihydro-1,4,2-oxathiazines and their oxides said to be useful as herbicides, plant fungicides, plant dessicants and defoliants. No mention is made of preserving wood materials from damaging organisms.
Chemical Abstracts 103(1):2144u refers to fungicides containing phenyl-alpha-chloroacetamides said to be effective in industrial environments including paints, metal cutting fluids, and to prevent the growth of cellulose degrading fungus on treated wood.
Chemical Abstracts 102(16):133786g refers to resistance to biological attack in wood treated with epoxides. U.S. Pat. No. 4,562,185 refers to 1-oxo-3-aza-cyclopentane derivatives said to be useful as pesticides, especially systemic insecticides, effective against acarids and nematodes and showing residual activity on wood and clay.
U.S. Pat. No. 4,067,862 refers to a process for modification of polymeric materials with a nitrile sulfide. The modified polymers are said to have uses including decorative or protective coatings for wood.
World Patents Index 67-05105G/00 refers to fungicidal 2-mono substituted amino 1-azacycloalkene-1 compounds, said to have fungicidal activity in both plants and other organic materials including wood.
U.S. Pat. No. 4,977,186 refers to wood preservative and soil treatment compositions containing carbamates.
This invention relates to a compound of the formula 
wherein n is 0, 1 or 2; R1 is hydrogen, C1-C4 linear or branched alkyl, or benzyl; and
Q is: 
wherein R2, R3 and R4 are, individually, hydrogen, alkyl, alkoxy, alkylthio, alkoxycarbonyl, halogen, trihalomethyl, cyano, acetyl, formyl, benzoyl, nitro, alkoxyaminomethyl, phenyl, or phenylaminocarbonyl, wherein the alkyl or alkoxy moieties are all C1-C4, linear or branched, with the proviso that at least one of R2, R3 or R4 must be other than hydrogen; 
wherein R5, R6 and R7 are, individually, hydrogen, C1-C4 alkoxy, C1-C4 alkylthio, halogen, trihalomethyl, cyano, acetyl, formyl, benzoyl, nitro, phenyl, or phenylaminocarbonyl, with the proviso that at least one of R5, R6 or R7 must be other than hydrogen; 
wherein R8, R9 and R10 are, individually, hydroxyl, halo, C1-C12 alkyl, C5-C6 cycloalkyl, trihalomethyl, phenyl, C1-C5 alkoxy, C1-C5 alkylthio, tetrahydropyranyloxy, phenoxy, (C1-C4 alkyl)carbonyl, phenylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, carboxy or its alkali metal salt, (C1-C4 alkoxy)carbonyl, (C1-C4 alkyl)aminocarbonyl, phenylaminocarbonyl, tolylaminocarbonyl, morpholinocarbonyl, amino, nitro, cyano, dioxolanyl, or (C1-C4 alkoxy)iminomethyl; or 
xe2x80x83wherein X is oxygen or sulfur; Y is nitrogen, xe2x80x94CHxe2x80x94, or xe2x80x94C (C1-C4 alkoxy)xe2x80x94; and Rxe2x80x3 is hydrogen or C1-C4 alkyl.
The compounds of the present invention are useful for the long-term preservation of wood and composite wood materials against wood damaging and wood destroying materials.
The present invention also provides methods useful for the long-term preservation of wood and composite wood materials against wood damaging and wood destroying materials. For the purpose of this invention, a composite wood material is any product made from wood, including, but not limited to, plywood, pressed wood, chipboard, particle-board, wafer board, wood laminated material and the like.
In accordance with the present methods, a wood material is preserved by treatment with a fungicidally or bactericidally effective amount of an active agent represented by the formula below 
wherein n is 0, 1 or 2; R1 is hydrogen, C1-C4 linear or branched alkyl, or benzyl; and
R is:
(a) phenyl; naphthyl; phenyl substituted with 1-3 of the following substituents:
hydroxyl, halo, C1-C12 alkyl, C5-C6 cycloalkyl, trihalomethyl, phenyl, C1-C5 alkoxy, C1-C5 alkylthio, tetrahydropyranyloxy, phenoxy, (C1-C4 alkyl)carbonyl, phenylcarbonyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, carboxy or its alkali metal salt, (C1-C4 alkoxy)carbonyl, (C,-C4 alkyl)aminocarbonyl, phenylaminocarbonyl, tolylaminocarbonyl, morpholinocarbonyl, amino, nitro, cyano, dioxolanyl, or (C1-C4 alkoxy)iminomethyl;
pyridinyl; thienyl, preferably when n is not 2; furanyl; or thienyl or furanyl substituted with 1 to 3 of the following groups:
alkyl, alkoxy, alkylthio, alkoxycarbonyl, halogen, trihalomethyl, cyano, acetyl, benzoyl, nitro, formyl, alkoxyaminomethyl, phenyl, or phenylaminocarbonyl, wherein the alkyl or alkoxy moiety is C1-C4, linear or branched; or 
xe2x80x83wherein X is oxygen or sulfur; Y is nitrogen, xe2x80x94CHxe2x80x94, or xe2x80x94C (C1-C4 alkoxy)xe2x80x94; and Rxe2x80x3 is hydrogen or C1-C4 alkyl.
In further accordance with the present invention, there is provided a composition comprising a) a wood preservative amount of a compound of formula I or II, and b) a suitable carrier.
A preferred embodiment of the compounds of this invention are those compounds of formula I wherein R1 is hydrogen or C1-C4 alkyl; n is 1 or 2; R2, R3 and R4 are, individually, hydrogen, C1-C4 alkyl, halo, (C1-C4 alkoxy)xe2x80x94carbonyl, or cyano, with the proviso that at least one of R2, R3 and R4 must be other than hydrogen; R5, R6 and R7 are, individually, hydrogen, halo or cyano, with the proviso that at least one of R5, R6 and R7 must be other than hydrogen; R8, R9 and R10 are C1-C4 alkyl, C1-C4 alkoxy, nitro, halo, trihalomethyl, or (C1-C4 alkoxy)xe2x80x94carbonyl; X is sulfur; and Rxe2x80x3 is hydrogen.
More preferred are those compounds of formula I wherein R1 is hydrogen; n is 1 or 2; R2, R3 and R4 are, individually, hydrogen, methyl, ethyl, bromo, chloro, ethyl carboxylate, or cyano, with the proviso that at least one of R2, R3 and R4 must be other than hydrogen; R5, R6 and R7 are, individually, hydrogen, bromo, chloro or cyano, with the proviso that at least one of R5, R6 and R7 must be other than hydrogen; R8, R9 and R10 are methyl, ethyl, nitro, fluoro, chloro, or trifluoromethyl.
In a preferred embodiment of the method of the present invention, the compounds of structure II are substituted with R1 being hydrogen, n being one or two, and R has one or 2 of the following values:
phenyl, (C1-C6 alkyl)phenyl, halophenyl, dihalophenyl, biphenyl, (C1-C5 alkyloxy)phenyl, trihalomethylphenyl, nitrophenyl, phenyl substituted with (C1-C4 alkoxy)carbonyl, furanyl, furanyl substituted by ethyl carboxylate, cyano, chlorine, or bromine, thienyl, thienyl substituted with ethyl carboxylate, cyano, chlorine, or bromine, or (C1-C6 alkyl)nitrophenyl.
In a still further preferred embodiment of the method of this invention, R1 is hydrogen, n is one or two, and R is represented by:
4-chlorophenyl, 3-nitrophenyl, 3,4-dichlorophenyl, 3-fluorophenyl, 2-thienyl, 4-methylphenyl, 3-trifluoromethylphenyl, 3-ethanonephenyl, 3,5-dichlorophenyl, 4-trifluoromethylphenyl, 3-methyl-4-nitrophenyl.
In another preferred embodiment of the method of this invention, R1 is hydrogen, and R is 
wherein X is sulfur, Y is nitrogen or xe2x80x94CHxe2x80x94, and Rxe2x80x3 is hydrogen.
The compounds of formula I and II can be prepared utilizing the procedures described in U.S. Pat. No. 4,569,690, the disclosure of which is incorporated herein by reference, or the procedures described in Examples 1-8 below. That patent discloses detailed examples of the synthesis of several 3-aryl-5,6-dihydro-1,4,2-oxathiazines and their oxides by two methods: one utilizing aromatic aldehydes as starting materials and one using arylcarbodithioate esters. Either method is viable and may be understood by one skilled in the art of organic chemical synthesis.
The compositions of this invention include a suitable carrier. Generally, the carrier may be a liquid vehicle for dissolving or suspending the active wood preservative ingredient. The vehicle typically contains at least one of a diluent, an emulsifier, and a wetting agent.
In addition, the carrier may also include other adjuvants conventionally employed in wood preserving compositions, such as organic binding agents, additional fungicides, insecticides, auxilliary solvents, processing additives, fixatives, plasticizers, UV-stabilizers or stability enhancers, water soluble or water insoluble dyes, color pigments, siccatives, corrosion inhibitors, antisettling agents, anti-skinning agents, and the like.
The wood preservative composition is typically supplied as a preparation with the active ingredients dissolved or dispersed in a liquid vehicle or carrier material, such that the active chemical ingredient(s) comprise from about 0.001% by weight up to about 10% by weight of the total composition. More generally, the active fungicidal or bactericidal ingredients will comprise from about 0.1 to 5% by weight, and most often from about 1 to about 5% by weight. For most wood preservative applications, the liquid vehicle can constitute as little as 5% by weight of the preparation. The composition of the present invention can be provided as a ready for use product in the form of aqueous solutions and dispersions, emulsions, aerosol preparations and the like or as a concentrate. The concentrate can be used as is, for example, as an additive for plywood glues, or can be diluted prior to use with additional solvent or suspending agents.
The liquid vehicle is not a critical aspect of the present invention and any liquid that does not interfere with the bactericidal and fungicidal activities of the active ingredients and which is compatible with wood preserving applications potentially can be used in the present invention. Suitable diluents for the liquid vehicle include water and organic solvents including aromatic hydrocarbons such as xylene, toluene, high aromatic petroleum distillates such as solvent naphtha, distilled tar oil and mixtures thereof, alcohols such as butanol, octanol, and glycols, vegetable and mineral oils, ketones such as acetone, petroleum fractions such as mineral spirits and kerosene and the like.
The diluent of the liquid vehicle generally comprises an organic solvent or solvent mixture. The liquid vehicle may contain at least one polar solvent, such as water, in admixture with an oily or oil-like low volatility organic solvent, such as the mixture of aromatic and aliphatic solvents found in white spirits, also commonly called mineral spirits.
Oily or oil-like or organic solvents useful in the present invention preferably have a flash point above 28xc2x0 C. and a boiling range, at atmospheric pressure, between about 130xc2x0 C. to 250xc2x0 C. while low-volatility organic solvents preferably have a flash point above about 55xc2x0 C. and a boiling range, at atmospheric pressure, between about 180xc2x0 C. to 3500C. The liquid vehicle is selected to enhance penetration of the active ingredients into the wood or wood product being treated.
An aerosol preparation according to the invention is obtained in the usual manner by incorporating the active ingredients dissolved or suspended in a suitable solvent, in a volatile liquid suitable for use as a propellant, for example, the mixture of chlorine and fluorine derivatives of methane and ethane commercially available under the FREON trademark, or compressed air.
The balance of the composition may include additional ingredients known to be useful in wood preservatives and related products. Such ingredients include organic binding agents, such as alkyd resins; fixatives such as carboxymethylcellulose, polyvinyl alcohol, paraffin and the like; co-solvents, such as ethylglycol acetate and methoxypropyl acetate; and plasticizers such as benzoic acid esters and phthalates, for example, dibutyl phthalate, dioctyl phthalate, and diodecyl phthalate. Optionally, dyes, color pigments, corrosion inhibitors, chemical stabilizers or dryers such as cobalt octate and cobalt naphthenate also may be included depending on specific applications and user preference.
The organic binding agent can be a chemically drying organic binder-forming polymer or a physically drying organic binder forming solids by solvent evaporation. Alkyd resins are a suitable class of organic binding agents; others will be recognized by those skilled in the art. The organic binding agents may themselves be supplied in a liquid vehicle, and in that case the amounts referred to herein for the organic binder are on a solids basis.
As mentioned above, such additional ingredients may include additional fungicides and insecticides. Suitable additional fungicides would be apparent to one skilled in the art, and will vary according to application. Examples include those fungicides known to have wood preservation uses, such as azaconazole, dichlofluanid, acypetacs, propiconazole, imazalil, cyproconazole, hexaconazole, IPBC, isothiozolone, tolylfluanid, chlorotalonil, benzimadazoles, Cu-oxides and Cu-HDO. Suitable insecticides would also be apparent depending upon application, and could include, for example, chlorpyrifos, cypermethrin, fenvalerate, isofenphos, permethrin, silafluofen, deltamethrin, cyfluthrin and imidachloprid. Such additional ingredients are not essential to the practice of the present invention but are included in particular formulations to optimize overall effectiveness and ease of application. The specific examples of suitable constituents for a wood preservative preparation as enumerated above are not meant to be limiting and a wide variety of other possible ingredients will be recognized to one skilled in the art. Similarly, the quantity of such ingredients in any formulation is not critical and can be used in an amount conventionally employed for products designed to be used in wood preserving applications. Normally, the totally formulated compositions may contain from about 0.1% to 95% by weight, and more usually from about 1% to 50% by weight of these additional ingredients on a total solids basis.
The wood preservative composition can be applied by any of the techniques known in the art including brushing, spraying, dipping, and the like. Generally, to obtain an effective treatment, it should be efficient to apply between about 0.05 to 0.4 kilogram of the composition per square meter of wood surface area to be treated, which is equivalent to about 0.01 to 0.08 pound per square foot. An amount of about 0.1 to 0.2 kg/m2, or about 0.02 to 0.04 pound/square foot, is more typical.
The active ingredient may also be applied in the wood by methods known in the art. Such methods include vacuum pressure impregnation, injection and diffusion. Suitable dose ranges for these methods include from about 0.01 to about 6.0 kg/m3 and preferably from about 0.5 to about 6 kg/m3, and more preferably from about 0.5 to about 1.5 kg/m3 of active ingredient in the treated wood.
The composition of the present invention can be prepared by mixing the various ingredients at a temperature at which they are not adversely affected, which usually will be from about xe2x88x925xc2x0 C. to 80xc2x0 C., preferably at a temperature of from about 10xc2x0 C. to 45xc2x0 C., and at a pressure of 450 mm Hg to 900 mm Hg, preferably at about 650 mm Hg to 850 mm Hg. Preparation conditions are not critical. Equipment and methods conventionally employed in the manufacture of coating compositions may be advantageously employed.
The following examples are presented for illustrative purposes and are not intended to limiting the scope of this invention in any manner.